Spectroscopic characterization of the first excited state and photochemistry of the HO3 radical.

Abstract

We report the one-dimensional cuts of the six-dimensional potential energy surfaces (PESs) of the ground and lowest doublet and quartet electronic states of trans-HO3 at the MRCI-F12/aug-cc-pVTZ level of theory. Theoretical calculations predict that the first excited state (A2A) presents a real minimum on its PES and possesses a nonplanar structure. The adiabatic excitation energy at the MRCI+Q and MRCI-F12 levels shows that the A2A state lies in the near-infrared region. Both the transition dipole moment and the oscillator strength were predicted to be weak, which suggests that photodissociation of HO3 to produce OH and O2 after UV-Vis absorption is not a plausible mechanism. The harmonic vibrational frequencies and rotational constants of the weakly bound complex OH-O2 in the two electronic states were predicted to help in its detection. Our PES shows that the reactions of H + O3 or HO2 + O in their ground states do not lead to trans-HO3 in its ground electronic state if one of the component fragments, i.e., HO2(A2A') + O(3P) or H(2S) + O3(3B2), is excited.